Determination of persulfate in emulsion polymerization latices

In the emulsion polymerization of butadiene, styrene, or both, potassium persulfate is often used as the catalyst. A convenient concentration of potassium persulfate in the aqueous layer of the charge is 0.10–0.2%; the method of analysis should therefore be suitable for very small persulfate concentrations. Three methods have been investigated. In the volumetric method the persulfate is allowed to react in an acid medium with an excess of standard ferrous iron, the excess being back-titrated after a given period of time with standard ceric cerium solution. The recommended procedure was found accurate and precise within 0.5%, even at such small concentrations as 5 mg. of potassium persulfate per 100 ml. When latex is analyzed by this method, the polymer is first removed by coagulation with sulfuric acid and the persulfate determined in the filtrate. In order to obtain reliable results the reaction between the persulfate and ferrous iron in the filtrate must be carried out in the absence of oxygen, although this is not necessary in solutions of pure persulfate. The interference by oxygen is attributed to substances of peroxidic character in the fatty acid soaps used as emulsifiers in the emulsion polymerization. The colorimetric method (“Becco” method) is based upon the oxidation of the leuco base of commercial wool green BSMA to a green dye by the persulfate and (colorimetric) measurement of the dye formed. The various factors affecting the accuracy and precision of this method have been investigated and a procedure is given for the analysis of latex. For several reasons, the volumetric and polarographic methods are superior to the colorimetric method. Persulfate in a latex can be determined accurately by polarographic analysis of the latex filtrate after removal of the polymer with sulfuric acid. The polarographic determination can be carried out, in the presence of oxygen, with simple equipment. The method is rapid and precise.